Pigment Molecules Research Articles

Nonradiative Transitions in Media of Different Polarities and Their Modeling for 12′-Apo-β-Caroten-12′-Al and 8′-Apo-β-Caroten-8′-Al

The theory of nonradiative transitions, based on the model of orientational broadening of electronic levels, is used to interpret known data on the effect of the polarity of the medium and temperature on the lifetime of the S 1(A − ) state for 12′-apo-β-caroten-12′-al and 8′-apo-β-caroten-8′-al. The effect of promoting vibrations on the rate constant for nonradiative transitions is considered. The results make it possible to hypothesize that the internal electric field created by the environment strongly perturbs the pigment molecules. Consequently, in the excited S 1(A − ) state, both pigments exist as different conformers I and II. Their structures differ by a 180° rotation of the cyclohexene ring relative to the polyene chain. Conformer II predominates in polar media, and is found in an intramolecular charge-transfer state S 1(A − /ICT). In addition, as a result of fluctuations in the internal electric field, it can also be found in a charge-separated state S 1(A − /CS).

Tailoring Pigment Dispersants with Polyisobutylene Twin-Tail Structures for Electrowetting Display Application

We have designed a class of highly hydrophobic dispersants for finely dispersing carbon black and organic pigment nanoparticles in apolar mediums. The synthesis involved the use of polyisobutylene-g-succinic anhydride (PIB-SA) and judiciously selected amines by amidation and imidation. The structures were characterized by infrared spectroscopy for anhydride functionalities in the starting materials and amide/imide linkages in the products. These polymeric forms of dispersants were structurally varied with respects to their PIB molecular weight, twin-tails, and linkages. Their relative performance for dispersing six different pigments in decane was evaluated against solution homogeneity, viscosity, stability, and particle size. The fine dispersion was achieved at particle sizes of ca. 100 nm, with the viscosity as low as 2-3 cP. The measurement of zeta potentials, which varied from -39.8 to -5.1 mV with pigment addition, revealed a strong surface-charge interaction between pigment and PIB dispersant molecules. Examination by TEM (transmission electronic microscope) showed the homogeneous dispersion of the primary structures of pigment particles at ca. 20 nm in diameter. The polymeric dispersants with different PIB tails and imide functionalities could be tailored for pigment stability in the oil phase, which is potentially suitable for the electrowetting devices.

Optical transitions in the light-harvesting complexes of bacterial photosynthetic centers

The geometric parameters of the model structure of the bacterial photosynthetic center, which consists of a light-harvesting antenna complex, a reaction center, lipid layers, and the solvation shells of water molecules, were optimized using quantum mechanics-molecular mechanics (QM/MM). The optical absorption spectra of the bacteriochlorophyll were evaluated in the quantum subsystem. It was shown that the shift of the absorption bands towards longer wavelengths as compared to the spectrum of the individual bacteriochlorophyll molecules is characteristic of the cluster of pigment molecules that are found in the antennas.

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces.

Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP.

Directional sensitivity of the retina: A layered scattering model of outer-segment photoreceptor pigments.

Photoreceptor outer segments have been modeled as stacked arrays of discs or membrane infoldings containing visual pigments with light-induced dipole moments. Waveguiding has been excluded so fields diffract beyond the physical boundaries of each photoreceptor cell. Optical reciprocity is used to argue for identical radiative and light gathering properties of pigments to model vision. Two models have been introduced: one a macroscopic model that assumes a uniform pigment density across each layer and another microscopic model that includes the spatial location of each pigment molecule within each layer. Both models result in highly similar directionality at the pupil plane which proves to be insensitive to the exact details of the outer-segment packing being predominantly determined by the first and last contributing layers as set by the fraction of bleaching. The versatility of the microscopic model is demonstrated with an array of examples that includes the Stiles-Crawford effect, visibility of a focused beam of light and the role of defocus.

Polypeptides and Oligonucleotides with Pendant Porphyrins : From Host-Guest Recognition to Self-Organizing Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short a-helical polypeptides.1 When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached within the cell membrane, where the solar energy is converted into chemical energy used by the cell to grow. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls, which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires.2 In order to mimic the light harvesting antennae of the photosynthetic system, we prepared porphyrin-functionalized a-polypeptides such as an octamer and an hexadecamer.3 The polypeptidic backbone confers, after a certain degree of oligomerization, the establishment of a 310 helical secondary structure. Such a conformation, favored by the natural tendency of the porphyrins to aggregate, induces an overlap of the chromophores, which thus present sufficient electronic coupling to promote a good exciton migration within the molecular wire.4 The 310helical secondary structure of this polypeptides generates three stacks of porphyrins pointing in three different positions of space with an angle between these three piles of about 120°. We recently synthesized a new family of polypeptides in which one porphyrin out of four is replaced by a porphyrin functionalized by a crown ether capable of complexing ammonium groups. All the crown ether functions thus point in one direction of space, being ready for molecular recognition with complementary molecules bearing ammonium groups. These results pave the way towards the preparation of pH dependant new type of glues. The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide viahost/guest interactions. We thus took advantage of these kind of host/guest interactions to assemble two poplypeptidic stains, opening the way to another type of novel glues. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498.a) R. W. Wagner, J. S. Lindsey, J. Seth, V. Palaniappan, D. F. Bocian, J. Am. Chem. Soc. 1996, 118, 3996-3997 and ref. cited therein. b) M. J. Crossley, P. L. Burn, S. J. Langford, J. K Prashar, J. Chem. Soc., Chem. Commun. 1995, 1921-1923. c) A. Osuka, H. Shimidzu, Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137.N. Solladié, A. Hamel, M. Gross, Tet. Lett. 2000, 41, 6075-6078.a) M. Fujitsuka, M. Hara, S. Tojo, A. Okada, V. Troiani, N. Solladié, T. Majima, J. Phys. Chem B. 2005, 109, 33-35. b) M. Fujitsuka, D. Won Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350.

Polypeptides with Pendant Porphyrins: From the Recognition of Bidentate Bases to Inter-Digitated Photo-Active Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short a-helical polypeptides.1 When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached within the cell membrane, where the solar energy is converted into chemical energy used by the cell to grow. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires.2 An octapeptide3 and an hexadecapeptide4 derived from the L-lysine and functionalized with porphyrins have been prepared. Beyond a certain degree of oligomerisation, we observed the development of a secondary structure such as a 310 helix which forces the porphyrins to arrange in a defined spatial arrangement. Due to the overlap of the porphyrins in such a conformation, the chromophores undergo a sufficient electronic coupling to favor a good exciton migration.5 The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide viahost/guest interactions. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498.a) R. W. Wagner, J. S. Lindsey, J. Seth, V. Palaniappan, D. F. Bocian, J. Am. Chem. Soc. 1996, 118, 3996-3997 and ref. cited therein. b) M. J. Crossley, P. L. Burn, S. J. Langford, J. K Prashar, J. Chem. Soc., Chem. Commun. 1995, 1921-1923. c) A. Osuka, H. Shimidzu, Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137. N. Solladié, A. Hamel, M. Gross, Tet. Lett. 2000, 41, 6075-6078.Unpublished results.a) M. Fujitsuka, M. Hara, S. Tojo, A. Okada, V. Troiani, N. Solladié, T. Majima, J. Phys. Chem B. 2005, 109, 33-35. b) M. Fujitsuka, D. W. Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350.

Spectral and kinetic parameters of phosphorescence of triplet chlorophyll a in the photosynthetic apparatus of plants.

Spectral and kinetic parameters and quantum yield of IR phosphorescence accompanying radiative deactivation of the chlorophyll a (Chl a) triplet state were compared in pigment solutions, greening and mature plant leaves, isolated chloroplasts, and thalluses of macrophytic marine algae. On the early stages of greening just after the Shibata shift, phosphorescence is determined by the bulk Chl a molecules. According to phosphorescence measurement, the quantum yield of triplet state formation is not less than 25%. Further greening leads to a strong decrease in the phosphorescence yield. In mature leaves developing under normal irradiation conditions, the phosphorescence yield declined 1000-fold. This parameter is stable in leaves of different plant species. Three spectral forms of phosphorescence-emitting chlorophyll were revealed in the mature photosynthetic apparatus with the main emission maxima at 955, 975, and 995 nm and lifetimes ~1.9, ~1.5, and 1.1-1.3 ms. In the excitation spectra of chlorophyll phosphorescence measured in thalluses of macrophytic green and red algae, the absorption bands of Chl a and accessory pigments - carotenoids, Chl b, and phycobilins - were observed. These data suggest that phosphorescence is emitted by triplet chlorophyll molecules that are not quenched by carotenoids and correspond to short wavelength forms of Chl a coupled to the normal light harvesting pigment complex. The concentration of the phosphorescence-emitting chlorophyll molecules in chloroplasts and the contribution of these molecules to chlorophyll fluorescence were estimated. Spectral and kinetic parameters of the phosphorescence corresponding to the long wavelength fluorescence band at 737 nm were evaluated. The data indicate that phosphorescence provides unique information on the photophysics of pigment molecules, molecular organization of the photosynthetic apparatus, and mechanisms and efficiency of photodynamic stress in plants.

Photo-Physical Properties of Simple and Double Strand Multi-Porphyrinic Polypeptides

One of our research field concerns porphyrin-functionalized a-polypeptides to control the spatial organization of the chromophores and enable exciton migration through the pool of porphyrins to mimic the light harvesting antennae of the photosynthetic system.1 In the photosynthetic system, the solar energy is collected by pigment molecules attached to the light harvesting complexes, in which the chlorophylls are held in a parallel orientation by fairly short a-helical polypeptides. When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached.1 Succeeding in organizing the porphyrins in a similar way as nature does should provide information about the relation existing between the orientation of the chlorophylls and the efficiency of nature in transferring an excited state over a very long distance and with minimal loss of energy.The right-handed 310 helical conformation adopted by our poly-L-lysine functionalized with eight porphyrins induces an overlap of the chromophores, which thus present sufficient electronic coupling to promote a good exciton migration within the molecular wire. We thus synthesized a good model of the light harvesting antennas of the photosynthetic system (studies realized in collaboration with Prof. T. Keiderling, University of Chicago, US and Prof. T. Majima, SANKEN, Osaka, Japan).2 Our peptides with pendant porphyrins were studied extensively throughout the world in collaboration with foreign colleagues, and found applications as organic photovoltaic cells,3 or redox molecular switches4 (studies realized in collaboration with Prof. S. Fukuzumi, Univeristy of Osaka, Japan and Dr. P. Ceroni, University of Bologna, Italy).These polypeptides with pendant porphyrins also found applications for the successful purification of Single-Walled Carbon Nanotubes (studies realized in collaboration with Prof. S. Fukuzumi, Univeristy of Osaka, Japan).5 Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498.M. Fujitsuka, D. W. Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350. T. Hasobe, K. Saito, P. V. Kamat, V. Troiani, H. Qiu, N. Solladié, K. S. Kim, J. K. Park, D. Kim, F. D'Souza, S. Fukuzumi, J. Mater. Chem. 2007, 39, 4160-4170.Paola Ceroni, Giacomo Bergamini, Nicolas Aubert, Vincent Troiani, Nathalie Solladié, Chem. Phys. Chem. 2005, 6, 2120-2128.Kenji Saito, Vincent Troiani, Hongjin Qiu, Nathalie Solladié, Takao Sakata, Hirotaro Mori, Mitsuo Ohama, Shunichi Fukuzumi, J. Phys. Chem. C 2007, 111, 1194-1199.

Atomistic Study of Energy Funneling in the Light-Harvesting Complex of Green Sulfur Bacteria

Phototrophic organisms such as plants, photosynthetic bacteria, and algae use microscopic complexes of pigment molecules to absorb sunlight. Within the light-harvesting complexes, which frequently have several functional and structural subunits, the energy is transferred in the form of molecular excitations with very high efficiency. Green sulfur bacteria are considered to be among the most efficient light-harvesting organisms. Despite multiple experimental and theoretical studies of these bacteria, the physical origin of the efficient and robust energy transfer in their light-harvesting complexes is not well understood. To study excitation dynamics at the systems level, we introduce an atomistic model that mimics a complete light-harvesting apparatus of green sulfur bacteria. The model contains approximately 4000 pigment molecules and comprises a double wall roll for the chlorosome, a baseplate, and six Fenna-Matthews-Olson trimer complexes. We show that the fast relaxation within functional subunits combined with the transfer between collective excited states of pigments can result in robust energy funneling to the initial excitation conditions and temperature changes. Moreover, the same mechanism describes the coexistence of multiple time scales of excitation dynamics frequently observed in ultrafast optical experiments. While our findings support the hypothesis of supertransfer, the model reveals energy transport through multiple channels on different length scales.

Evidence for Copigmentation Interactions between Deoxyanthocyanidin Derivatives (Oaklins) and Common Copigments in Wine Model Solutions

The aim of this study was to investigate interactions possibly taking place in red wine between oaklins, which are deoxyanthocyanidin derivatives (guaiacylcatechin-pyrylium and syringylcatechin-pyrylium), and several copigments: catechin (CP1), epicatechin (CP2), chlorogenic acid (CP3), epigallocatechin (CP4), and procyanidin B3 (CP5). The results show that oaklins, like common anthocyanins, also present copigmentation interactions that further stabilize the flavylium cation in hydroalcoholic solutions. Molecular dynamics simulations were also performed to interpret the binding data, to specify the relative arrangement of the pigment and copigment molecules within the complexes, and to interpret their absorption properties in the visible range.

ChemInform Abstract: Optical and Physico‐Chemical Properties of Tetrapyrrole Molecules in Nanoporous Silicate Gel Matrices

In this mini-review, we present the main results of our works on the spectroscopy of the molecules of tetrapyrrole pigments incorporated into nanoporous gel matrices. Xerogels activated by organic dyes are promising materials for applications in various fields of technology. The influence of the technique of embedment of the activator molecules on their physico-chemical properties has been analyzed. The specificity of the action of a silicate matrix as external medium, as compared to liquid and solid solutions, is shown.

Optical and physico-chemical properties of tetrapyrrole molecules in nanoporous silicate gel matrices

In this mini-review, we present the main results of our works on the spectroscopy of the molecules of tetrapyrrole pigments incorporated into nanoporous gel matrices. Xerogels activated by organic dyes are promising materials for applications in various fields of technology. The influence of the technique of embedment of the activator molecules on their physico-chemical properties has been analyzed. The specificity of the action of a silicate matrix as external medium, as compared to liquid and solid solutions, is shown.

Structural Features of Copigmentation of Oenin with Different Polyphenol Copigments

The copigmentation binding constants (K) for the interaction of different copigments with oenin (major red wine anthocyanin) were determined. All tests were performed in a 12% ethanol citrate buffer solution (0.2 M) at pH 3.5, with an ionic strength adjusted to 0.5 M by the addition of sodium chloride. Over the past years, several copigmentation studies were made and many copigments were tested, but none of them included prodelphinidin B3 or a dimeric-type adduct like oenin-(O)-catechin, probably due to the difficulty in obtaining them. The data yielded from this study allowed concluding that (a) the presence of a pyrogallol group in the B ring of the flavan-3-ol structure slightly increases the copimentation potential and (b) within all copigments tested oenin-(O)-catechin was revealed to be the best. According to computational studies performed on epicatechin/oenin, epigallocatechin/oenin, procyanidin B3/oenin, and oenin-(O)-catechin/oenin complexes, the ΔGbinding energy of the oenin-(O)-catechin/oenin complex is the most negative compared to the other copigmentation complexes, hence being more stable and thermodynamically favored. All structural data show that oenin-(O)-catechin and epigallocatechin are closer to the pigment molecule, which is in accordance with these two copigments having the highest experimental copigmentation binding constants for oenin.

The Study in the Application of Nanotechnology Digital Printing in Clothing Pattern Design

Nanotechnology, in the 21st century, is the biggest driving force in the development of technology and industry, which has its wide range of applications. In traditional industries, nanotechnology can be applied to the development of digital printing ink. Digital printing appears as a new printing technology in the 1990s, the 20th century. And in recent years, along with the trends of a global energy saving and carbon reduction, the concept of producing green products with low-carbon, water saving, energy abating, pollution decreasing attributes has arisen. The introduction of digital printing to textiles brings the speed, flexibility, wide areas of color selection, environmental protection and the potential of cost saving etc; the technology becomes a major breakthrough in the textile printing industry. The industry is committed to the technology of environmental friendly digital printing and goes toward to a new pattern of bright future in fashion design. While the globe puts effort to develop digital printing, the core technology should not only focuses on how to come up with high-speed, large amount, low-cost machines, but also the R & D to the making and applications of digital printing, which has a great impact on digital printing quality. At the present, the digital printing ink of the reactive ink / acidic ink is applied to cotton fabrics and the fabrics containing hemp content. The printing process is from the fabric pretreatment → inkjet printing →solid color processing → washing → drying. Moreover, sublimation transfer ink is applied to fabrics containing polyester fiber content; but it cannot be fully colored the fabrics of general 100% cotton and silk, which is the biggest drawback of this sublimation transfer ink. Therefore, this study, primarily through the Nanotechnology with green environmental protection and reduction of carbon from Mimaki Engineering Co., Ltd., captures the moral of the cultural patterns of the local characteristics by the techniques of changing, modeling, designing, and arranging on the patterns of dress design. And it uses computer graphics software, Adobe Photoshop & Illustrator, to draw and trim the separate pattern and the foursquare consecutive pattern for the completion of fashion pattern designs. And it applies the features of the nano pigment ink on the fabrics of cotton, hemp, silk, and polyester fiber to interpret the artistic style of the local through digitized programming language. The importing of nanotechnology refills new sources of industrial competition. This study expects to explore the nanotechnology digital printing and combine with the design of the clothing pattern transforming on the designs, grinding pigment molecules to nano ultra-fine level with reduced light scattering phenomena and good light purity. Fully demonstrating the features of natural bright color, the endurance of pigment water and the light fastness will be able to create a lager space of application and market in the digital printing industry.

Anchored LH2 Complexes in 2D Polarization Imaging

Protein is a soft material with inherently large structural disorder. Consequently, the bulk spectroscopies of photosynthetic pigment protein complexes provide averaged information where many details are lost. Here we report spectroscopy of single light-harvesting complexes where fluorescence excitation and detection polarizations are both independently rotated. Two samples of peripheral antenna (LH2) complexes from Rhodopseudomonas acidophila were studied. In one, the complexes were embedded in polyvinyl alcohol (PVA) film; in the other, they were anchored on the glass surface and covered by the PVA film. LH2 contains two rings of pigment molecules-B800 and B850. The B800 excitation polarization properties of the two samples were found to be very similar, indicating that orientation statistics of LH2s are the same in these two very different preparations. At the same time, we found a significant difference in B850 emission polarization statistics. We conclude that the B850 band of the anchored sample is substantially more disordered. We argue that both B800 excitation and B850 emission polarization properties can be explained by the tilt of the anchored LH2s due to the spin-casting of the PVA film on top of the complexes and related shear forces. Due to the tilt, the orientation statistics of two samples become similar. Anchoring is expected to orient the LH2s so that B850 is closer to the substrate. Consequently, the tilt-related strain leads to larger deformation and disorder in B850 than in B800.

Architecture and function of plant light-harvesting complexes II

The antenna system associated with plant photosystem II (PSII) comprises a series of light-harvesting complexes II (LHCIIs) which are supramolecular assemblies of chlorophylls, carotenoids, lipids and integral membrane proteins. These complexes not only function in capturing and transmitting light energy, but also have pivotal roles in photoprotection under high-light conditions through a mechanism known as non-photochemical quenching process. Among them, the most abundant major species (majLHCII) is located at the periphery of PSII and forms homo/hetero-trimers. Besides, three minor species, named CP29, CP26 and CP24, are adjacent to the PSII core, exist in monomeric form and bridge the majLHCII trimers with the core complex. Structural studies on majLHCII and CP29 have revealed the overall architecture of plant LHC family, the binding sites of pigment molecules and the distribution pattern of chromophores in three-dimensional space. The high-resolution structural data of LHCIIs serve as fundamental bases for an improved understanding on the mechanisms of light harvesting, energy transfer and photoprotection processes in plants.

A mechanistic model for the photosynthesis–light response based on the photosynthetic electron transport of photosystem II in C3 and C4 species

A new mechanistic model of the photosynthesis-light response is developed based on photosynthetic electron transport via photosystem II (PSII) to specifically describe light-harvesting characteristics and associated biophysical parameters of photosynthetic pigment molecules. This model parameterizes 'core' characteristics not only of the light response but also of difficult to measure physical parameters of photosynthetic pigment molecules in plants. Application of the model to two C3 and two C4 species grown under the same conditions demonstrated that the model reproduced extremely well (r(2) > 0.992) the light response trends of both electron transport and CO2 uptake. In all cases, the effective absorption cross-section of photosynthetic pigment molecules decreased with increasing light intensity, demonstrating novel operation of a key mechanism for plants to avoid high light damage. In parameterizing these previously difficult to measure characteristics of light harvesting in higher plants, the model provides a new means to understand the mechanistic processes underpinning variability of CO2 uptake, for example, photosynthetic down-regulation or reversible photoinhibition induced by high light and photoprotection. However, an important next step is validating this parameterization, possibly through application to less structurally complex organisms such as single-celled algae.

Quinacridone-Diketopyrrolopyrrole-Based Polymers for Organic Field-Effect Transistors.

Incorporation of pigment or dye molecules as building units is of great interest in the development of semiconducting polymers, due to their strong intermolecular interactions arising from the strong local dipoles in the unit structure, which would facilitate the charge transport property. In this paper, semiconducting polymers based on well-known pigments, namely, quinacridone and diketopyrrolopyrrole, are synthesized and characterized. The π-stacking distances are found to be 3.5–3.8 Å, which is fairly narrow for semiconducting polymers, indicating that they possess strong intermolecular interactions. Interestingly, polymer orientation is influenced by the composition of alkyl side chains. While the edge-on orientation is observed when the linear alkyl groups are introduced for all the side chains, the face-on orientation is observed when the branched alkyl groups are introduced either in the quinacridone or diketopyrrolopyrrole unit. It is found that the electronic structure of the present polymers is mostly affected by that of the diketopyrrolopyrrole unit, as evidenced by the absorption spectra and computation. Although the field-effect mobility of the polymers is modest, i.e., in the order of 10−4–10−3 cm2/Vs, these findings could be important information for the development of semiconducting polymers.

Rapid detection of haloarchaeal carotenoids via liquid–liquid microextraction enabled direct TLC MALDI-MS

For the first time, we demonstrate the use of TiO2 nanoparticles (NPs) for enhancing the carotenoid production by the extremophilic haloarchea, Haloferax mediterranei. TiO2 NPs at optimal concentration of 375mg/L results in a 95% increase in the production of carotenoid pigment compared to the control (no TiO2 NPs). The carotenoid pigments extracted from TiO2 NPs treated H. mediterranei cells, were separated using thin layer chromatography (TLC). The separated carotenoid spots were subjected directly for MALDI MS detection. To limit the sample diffusion during matrix addition on TLC plates, a simple bordering mode was exercised. Using this method we were able to detect the pigments successfully using MALDI-MS, directly from TLC plates after separation. In addition, we also applied the Pt NPs capped with ODT via Liquid–liquid microextraction (LLME) for extracting the pigment molecules from the halobacteria in MALDI-MS. These novel NP approaches possess numerous advantages such as; rapidity, ease in synthesis, high sensitivity and low cost.